Production of organophosphorus compounds



United States Patent PRODUCTION OF ORGANOPHOSPHORUS COMPOUNDS Charles w. Weber, jersey City, N.J., assign to The M; W; Kellogg Company, Jersey City, N..I., a corporation of Delaware No Drawing. Application October 30, 1953 Serial No. 389,483

14 claims. (or. 260 543) This invention relates to a new and improved process for the production of organophosphorus compounds. In one aspect this invention relates to the production of organic phosphonyl halides and the corresponding phosphonic acids and derivatives derived therefrom. In another aspect this invention relates to the production of organic phosphine oxides. In a still more particular aspect this invention relates to the production of methane phosphonyl dichloride.

The organic phosphonyl halides and especially methane phosphonyl dichloride, as well as the organic phosphine oxides, are much in demand as inter-mediate chemical reactants for the production of more complex organic phosphorus compounds, such as the corresponding esters, free acids and amides by conventional methods, which are useful as fungicides, insecticides, pharmaceuticals, petroleum additives for improving lubricating oils and polymer additives. Prior to the present invention, relatively low molecular weight organic phosphonyl halides and phosphine oxides have been obtained by devious and round about methods involving numerous chemical and mechanical steps. Less involved methods for the production of organic phosphonyl halides, for example, are not applicable to the production of low molecular weight analogs in good yields. Methane phosphonyl dichloride is a particularly difiicult compound to produce. For example, the reaction between methane, phosphorus trichloride and oxygen is a very poor reaction and produces methane phosphonyl dichloride in very low yield, although higher molecular weight alkanes, such as n-heptane react with phosphorus trichloride and oxygen to produce the corresponding alkane phosphonyl dichlorides in somewhat better yields.

It is therefore an object of the present invention to provide a new and improved process for producing organic phosphonyl halides and organic phosphine oxides.

Another obje'c't is to produce such organophosphorus compounds with the minimum formation of byproducts and with the maximum utilization of reactants.

/ Still another object is to provide a novel direct method for the production of organic phosphonyl halides and organic phosphine oxides.

7 Still another object of this invention is to provide an effective and economical process by which such organo phosphorus compounds may be prepared in high yield with good selectivity.

Another object is to provide a new and improved catalyst for use in the production of organo phosphorus compounds. I v

A further object is "to provide a direct method for the production of methane phosphonyl dichloride in high yield with good selectivity.

Various other objects and advantages of the present invention will become apparent to those skilled in the art from the accompanying description and disclosure.

In accordance with this invention organophosphorus compounds ofthe general formula R P=O including orphos'phoiiyl dihalides, organic phosphonyl monohalides and organic phosphine oxides are produced by a process which comprises reacting under appropriate conditions an organic ether, an organic halide and a trivalent phosphorus halide in the presence of a catalyst mixture comprising iodine and a metal phosphorus trihalo complex. The R groups of the general formula for the organophosphorus compounds produced in m cordance with this invention represent halogens (F, Cl, Br and I) and organic radicals and at least one R is an organic radical. Where more than one organic radical is included in the product, or more than one halogen is included in the product, these organic radicals "and halogens may be the same or different.

The phosphorus trihalo complex of the catalyst mixture includes any metal phosphorus trihalo complex of the general formula M(PX where X is chlorine, bromine, iodine or fluorine and M is a metal selected from groups VI and VIII of the periodic table, such as chromium, iron, cobalt, nickel, molybdenum, ruthenium, rhodium, tungsten, rhenium, osmium and iridium and n is a number equal to at least twice the minimum valence of the metal involved.

Examples of such phosphorus trihalo complexes are. cobalt tetrakistrichlorophosphine, iron penta-trichloro phosphine, nickel tetrakistribromophosphine, nickel tetra kistrifluorophosphine, cobalt tetrakistribromophosphine and osmium penta-trichloroph'osphine.

The metal phosphorus trihalo complexes may be pre pared in a manner similar to the following as illustrated for nickel tetrakistrichlorophosphine. Nickel carbonyl is reacted with excess phosphorus trichloride by heating on a steam bath under reflux conditions. Excess P01 is removed by distillation. The remainder is dissolved in pentane and cooled to 60 C. in an atmosphere of carbon dioxide to precipitate the product.

It is within the scope of this invention to form the metal phosphorus trihalo complex in situ in the reaction zone by introducing the appropriate metal carbonyl with the reactants including phosphorus trihalide.

The use of the metal phosphorus trihalo complex ma terially reduces the amount of iodine required as a cat alyst to obtain comparable yields of product. As a re sult the present process is cheaper with respect to both initial cost of catalyst and recovery and purification of product to free it from free iodine formed during the reaction.

Examples of suitable iodine-containing catalysts which may be used in accordance with this invention are: metal iodides, such as nickel iodide, zinc iodide, cobalt iodide, sodium iodide, aluminum iodide and manganese iodide; phosphorus iodides, such as phosphorus di-iodide and phosphorus tri-iodide; and free iodine.

The organic ethers to be employed in accordance with this invention are selected from the group consisting of the saturated unsubstituted and substituted alkyl ethers, including the acyclic and alicyclic alkyl ethers. The substituted alkyl ethers contain substituents selected from the group consisting of the halogens, nitro group, cyano group and aryl groups. It is preferable to employ ethers in which each of the organic radicals linked to the ether oxygen atom contains not more than 10 carbon atoms. Ethers which give satisfactory yields of product are the symmetrical ethers (R'OR) in which the organic radicals (R) are the same and correspond to the organic radicals of the final products. Typcial examples of the symmetrical ethers are dimethyl ether, diisopropyl ether, dibenzyl ether, alpha, alpha'-dichloro dimethyl ether, beta, beta-oxy diproprio nitrile and beta, beta'-dinitro dipropyl ether. The ethers in which the organic radicals (R) linked to the oxygen atom are difierent may also be em ployed. When an unsymmetrical ether which is nee of alpha halo substitution is used, the products are mixed products corresponding to the alkyl and cycloalkyl radicals of the ethers- Typical examples of such unsymmetrical ethers are methyl ethyl ether, ethyl benzyl ether, methyl cyclohexyl ether, propyl t-butyl ether and betachloroethyl benzyl ether. The mono-alpha halogenated ethers, such as those with the general formula 1 I Iv -011 011" I in which R" is hydrogen or an alkyl radical and X is a halogen (F, Cl, Br and I) have been found to give high yields of organic phosphonyl halides (R'li -X R'zIF-X) and organic phosphine oxides (R' P=O) when employed according to this invention. Typical examples of a few of such halogenated ethers are: chloromethyl methyl 'ether, iodomethyl methyl ether, alpha-fluoroethyl propyl ether, alpha-chloroethyl propyl ether, bromomethyl isoamyl ether, chloromethyl beta-chloroisopropyl ether and alpha-bromoethyl ethyl ether. Other types of ethers may also-be employed, examples of which are as follows: straight chain polyethers, such asdimethoxy methane and diethoxyethane, cyclic monoethers, such as tetrahydrofuran, and cyclic polyoxy ethers, such as dioxane and trioxane. Mixtures of various ethers may be used also but in such a case there are obtained mixtures of products which may be separated, however, by conventional techniques, such as fractional distillation.

The organic halides employed according to this invention are the unsubstituted and substituted hydrocarbon halides, such as the alkyl, including both acyclic and alicyclic, and aromatic halides, preferably having less than fifteen carbon atoms per molecule. The substituted alkyl halides are preferably those in which one or more hydrogen atoms is substituted by a corresponding number of radicals selected from the group consisting of the halogens, nitro group, cyano group, aryl groups, and sulfone group. The aromatic halides are those in which the halogen atom is activated by the presence of a nitro group, preferably at least two in the ortho and para'positions of the aromatic ring. The following compounds are given as examples of suitable organic halides which may be used by this novel process and are in no way to be construed as limiting the scope of this invention: methyl chloride, methylene dichloride, ethyl bromide, isopropyl chloride, isoamyl chloride, cyclopentyl chloride, chloromethyl nitrile, hexachlorocyclohexane, tetradecyl chloride, carbon tetrachloride, trichloromethyl bromide, 1,1- difluoro-1-chloro-2,2,Z-trichloroethane, cyclohexyl bromide, hexachlorohexane, methyl iodide, benzyl iodide, isopropyl fluoride, fluorobenzo dichloride, 2-cyano-1-chloroethane, Z-nitropropyl chloride, trichlorocyanopropane,

nitrotrichloromethane, benzyl chloride, 2-4-dinitrochlorobenzene, para-nitrochlorobenzene, 2,4-dinitrobromobenzene, phenyl fi-chloropropyl sulfone, and phenyl ,3- chloroethyl sulfone. Mixtures of different organic halides may be used in accordance with this invention and in such case mixtures of products will be obtained. Although any of the halogens are suitable as the halogen of the organic halide, the gaseous halogens are preferred and chlorine has been found to be the most preferable and the more economical of the halogens. The alkyl halides may be prepared in conventional manner known to those skilled in the art.

Both inorganic and organic trivalent phosphorus halides may be used as the phosphorus halide reactant of the present invention. Typical examples of inorganic trivalent phosphorus halides are as follows: phosphorus trifluoride, phosphorus trichloride, phosphorus tribromide and phosphorus triiodide; mixed phosphorus halides, such as difluorophosphorus chloride, difluorophosphorus iodide. dichlorophosphorus fluoride, chlorobromophosphorus fluoride and dichlorophosphorus bromide; and diphosr phorus tetraiodide. The preferred organic trivalen phosphorus halides which may be .used in accordance with this invention are the hydrocarbon phosphorus halides having only a continuous carbon skeleton of not more than 15 carbon atoms, such as the acyclic and alicyclic alkyl phosphorus halides, either substituted or unsubstituted, and the aromatic phosphorus halides, either substituted or unsubstituted. In general, the organic radical of the organic phosphorus halide is selected from the same classes'as the organic halides previously discussed, and may be the same or difierent than the organic radical of the organic halide. Typical examples of organic phosphorus halides are methyl phosphorus dichloride, ethyl phosphorus difluoride, isopropyl phosphorus dichloride, benzyl phosphorus dichloride, phenyl phosphorus diiodide, diphenyl phosphorus chloride, diphenyl phosphorus bromide, 4-nitrophenyl phosphorus dibromide, 4-bromophenyl phosphorus dichloride, di(4-nitrophenyl) phosphorus chloride, methyl ethyl phosphorus chloride, methyl ethyl phosphorus bromide, diethyl phosphorus bromide, dibenzyl phosphorus chloride, dipropyl phosphorus chloride, cyclohexyl phosphorus dichloride, cyclopentyl phosphorus dibromide, beta-chlorooctyl phosphorus dichloride and cyclooctyl bromo phosphorus chloride. The halogen of the trivalent phosphorus halide may be any of the halogens, preferably the gaseous halogens, such as chlorine, without departing from the scope of the invention.

Alkoxy phosphorus halides having the general formulae RO.PX and (R'O) PX may also be used as a reactant in accordance with this invention. Such alkoxy phosphorus halides are used in addition to one or more of the above type of trivalent phosphorus halide. When using organic phosphorus halides in which there is present one or more phosphorus to carbon bonds, such bonds remain intact during the course of the reactions described herein and each ofthe organic radicals may be present in the final product. When alkoxy phosphorus halides are employed, the oxygen to phosphorus bond is cleaved during the course of the reaction and the final product will not contain the RO-radicals as such. Thus in order to obtain the maximum utilization of such alkoxy phosphorus halides it is preferable for the organic group of the RO-radical to be the same as the organic group of the organic halide reactant, Typical examples of such alkoxy phosphorus halides are methoxy phosphorus dichloride, ethoxy phosphorus dibromide and dimethoxy phosphorus chloride.

The particular trivalent phosphorus halide employed depends upon the ultimate product desired. When producing an organic phosphonyl dihalide an inorganic phosphorus trihalide (PXa), or a trivalent organic phosphorus halide of the above classes, is em ployed. When producing an organic phosphonyl monohalide, such as methyl phenyl phosphonyl chloride, an organic phosphorus dihalide, such. as phenyl phosphorus dichloride is employed. Further when producing a phosphine oxide in which the three organic radicals may or may not .be the same, an organic phosphorus monohalide of the type R' PX (wherein the R's may or may not be the same, and may or may not be the same as the R radical of the organic ether and organic halide reactants) is used.

The aliphatic and aromatic phosphorus halides may be prepared by reacting a phosphorus trihalide, such as the trichloride, .with a dialkyl, dicycloalkyl, or diacyl mercury derivative at a temperature of'180 C. to 230 C. The dihalides are first produced and by continuing the heating for a further length of time the monohalide may be produced and recovered. The aromatic phosphorus halides may also be produced by reacting an aromatic hydrocarbon with a of a Frkdfl-Crafis catalyst, such as aluminum chloride.

phosphorus trihalide in the presence assesse- Althou'gh: the yield of organophosphorus compound pfodilced by the reaction which comprises reacting an organic halide, an organic ether and a trivalent phospadres halide is satisfactory, the yield of organophosphorus compound produced may be substantially increased by" the presence inthe reaction mixture of a compound containing a phosphoryl group. The exact mechaiiis'hi of'tlie reaction described herein is not known. It is postulated" without limiting the invention, however, that when. a compound containing a phosphoryl group is used in accordance withthis invention it is serving as one of the sources of oxygen in the final product. In view of this, therefore, a wide variety of compounds containing the phosphoryl group may be: used in accordance with. this invention, including both inorganic and organic phosphoryl compounds. The preferred phosphoryl comoounda are the'inorganic phosphoryl trihalides it Q P-Xa) Typical examples of suitable phosphoryl trihalides are phosphoryl trifiuoride, phosphoryl. trichloride, phosphoryl tfib'romide and the mixed phosphoryl trihalides, such as bfomo phosphoryl dichloride, dichl'oro phosphoryl fluoride and; iodo phosphoryl dichloride. Examples of organic phosphoryl compounds which give satisfactory yields of product are chloromethane phosphonyl dichlodiethyl' phosphonyl chloride, benzene phosphonyl dichloride and organic phosphates, such as trimethyl phosphate. Phosphoryl trichloride' and phosphoryl tribromide have been found to be the more economical and convenient of the various phosphoryl compounds whichmaybe em loyed. p v The organic phosphonyl halide reactants may be prodated by reacting the corresponding phosphonic acid with phosphorus pentahalide, such as the pentachloride, at room temperature. Aliphatic phosphonyl halides. having at least 5 carbon atoms may also be produced by reacting an aliphatically bound hydrogen atom of a hydrocarbon with phosphorus trihalide, such as the trichloride, by blowing. free oxygen through the reaction mixture at room temperature.

In g'eneral the organic reactants may include as much as lj 5'carbon atoms in the molecule and in a single chain, preferably, however, the number of carbon atoms per molecule and in a single carbon chain is not more than 8. The total catalyst mixture is generally employed in an amount between about 0.01 mole and about 1.5 moles per mole of trivalent phosphorus halide. Preferably, between about 0.02 mole and about 0.5 mole of total catalyst mixtitre is employed per mole of trivalent phosphorus halide. Usually no more than about 0.1 mol of the iodine component per mole of phosphorus halide is required and the amount may be as low as 0.002 mol per mole of phos phorus halide. Small amounts of phosphorus triiodide and methyl iodide, although classed as reactants may act as catalysts when other reactants are used as the principal reactants. The mole ratio of the iodine component to the metal phosphorus trihalo complex of the catalyst is etlween about 1:100 and about 1:1; preferably 1:25 to 1:

The amount of phosphoryl compound which may be employed is not critical to the production of phosphonyl halides and phosphine oxides as described herein. The

mole ratio of phosphoryl compound to trivalent phosphorus halide may vary over a relatively wide range, such as between and about 5. When a phosphoryl compound is employed the preferable range is between about 0.2 mole and about 2 moles of phosphoryl compound per mole of trivalent phosphorus halide. Although amounts ofphosphoryl compound in excess of 5 moles may be Used. without seriouslyinterfering withthe formation of the desired organophosphorus compounds, the use of such excessiveamounts of this reactant is not necessary and 6 7 may only add to the"cost -o'f" production ofdesired products.

Generally the mole ratio of the organic ether reactant with respect to the trivalent phosphorus halide reactant will range from about 0.1 and about 0.8 or about 1.0. Similarly the mole ratio of the organic halide reactant wtih respect to the trivalent phosphorus halide can vary over a relatively wide range when producing phosphonyl halides and phosphine oxides ac cording to the present invention. In general the organic halide may be employed in an amount equal to about 0.1 mole to about 4.0 moles per mole of trivalent phosphorus halide, the preferable amount being between about 0.2 mole and about 2.5 moles of organic halide per mole of trivalent phosphorus halide.

Asstated previously organic phosphonyl halides and organic phosphine oxides may be produced by the reaction between an organic halide, an organic ether and. a trivalent phosphorus halide in the absence of a phosphoryl compound as illustrated by the following typical general reactions wherein only the chief reaction prod not is shown:

Other typical general reactions of this invention are the following, where for the purpose of simplicity, O=PE will be used to represent the phosphoryl group of the phosphoryl-containing compound and wherein only the chief reaction product will be shown:

The R, R" and R groups in the chemical formulas shown above represent organic radicals as previously discussed and may be the same or different, and X repre sents a halogen atom (Cl, F, Brand I).

The following equation for the production of methane phosphonyl dichloride by the reaction between chloromethyl methyl ether, methyl chloride, phosphorus trichloride and phosphoryl trichloride is cited as a typical specific example and is not to be construed as limiting the scope of the present invention:

' ll Cl-CHz-OCH3 CHzCl P01: P001: CHzPCh The process of this invention may be conducted in batchwise or continuous systems, or as a stepwise re action. When a catalyst is employed the reaction of the process described herein may be conducted as a multistage reaction, but preferably as a two-stage reaction. The first stage is the reaction of an organic ether, an organic halide and a trivalent phosphorus halide with or without the addition of a phosphoryl compound in the presence of the catalyst mixture of the present invention. The second and subsequent stages are the reaction of the total crude product obtained in the first step with additional amounts of the same reactants with or without the addition of more catalyst mixture. In so conducting the reaction in this stepwise manner improved yieldsiof phosphonyl halides andphosphine oxides are obtained by using smaller amounts of catalyst mixture as compared to the amount of catalyst mixture needed when the reaction is conducted as a one-step reaction. The process of the present invention is operative at a temperature between about room temperature (20 C.) and the decomposition temperature of the reactants. ,Generally the temperature of the reaction will be below about 300 C. The reaction may be efiected at elevated temperatures by introducing the individual reactants, either separately or together, into a reaction zone, such as a steel bomb, and carrying out the reaction under autogenous conditions. of pressure as a matter of convenience. The preferred temperature range is between about 150 C. and about 275 C. The time of reaction may vary' over relatively wide limits, such as between about minutes and about 20 hours, but the preferable contact time or residence has been found to be between about 1 and about hours.

; Any free iodinewhich may be present upon completion of the reaction is conveniently separated by treating the crude product with mercury, followed by removal of the mercury salts. The products of the reaction are further purified by conventional methods, such as distillation or crystallization of solid products depending upon the physical nature of the products. Liquid products may be separated as almost one hundred percent pure by etlicient fractional distillation. The phosphonyl halides may be isolated as such or may be hydrolyzed to the corresponding phosphonic acids which may then be converted to various ester derivatives, or the phosphonyl halides may be converted directly to a desired type ester by conventional methods. These derivatives have many known uses to those skilled in the art as previously discussed. The products are identified by the usual methods, such as determination of boiling point and other such physical properties, de-

termination of infrared'absorption spectra, percent com position analysis, mass spectrometer analysis, etc.

The reaction may be efiected in the presence of liquid diluents or solvents, such as benzene, nitrobenzene, toluene and hexane, in which the reactants are dissolved or dispersed by mechanical agitation or byconventional emulsifying agents.

It is to be understood that the choice of temperature of reaction, contact time, molar quantities of reactants and catalyst mixture to be preferred in any instance will depend uponthe starting materials employed and the result desired, and that the procedure employed for the isolation and purification of desired products will be dependentupon the physical nature of the products. Although the theory and mechanism of reaction is believed to be correct, other theories may explain the reaction of the present invention, and the theories advanced herein are not to be construed as an unnecessary limitation on the invention.

The following examples are ofiered as a better understanding of thepresentinvention, but the examples are not to be considered as unnecessarily limiting the present invention:

' Example 1 'A 200 ml. steel bomb was charged with 23 ml. (0.3 mole) of chloromethyl methyl ether, 33.2 grams (0.66 mole) of methyl'chloride, 70 ml. (0.9 mole) of phosphorus trichloride, 27 ml. (0.3 mole) of phosphoryl trichloride and 46.9 grams (0.15 mole) of nickel iodide. The bomb was then closed, placed in a reciprocating shaker and heated to 250 C. and held at this temperature for a period of 7 hours. After cooling, the bomb was vented to atmospheric pressure. The total crude product in the bomb was transferred to a distilling flask and heated at atmospheric pressure. Two liquid fractions were obtained: thefirst fraction" had a boiling point of 41 C. to 121 C.; the second' fractionhad a boiling point of 121 C. to'1'833 C. Fhe low boiling fraction" was freed of iodine by shaking with mercury followed: by removalofthe mercury, salts by filtration; this fraction was found to be chiefly "unreacted' starting compounds. Th ,high boiling fraction was diluted with purified chloroform-shaken with mercury and filtered to remove the mercury salts. After removal of the chloroform from the highboiling fraction this fraction-was further purified by distillation at atmospheric. pressure. A liquid fraction weighing 60.4 grams and having a boiling point of vC. to Ci con. tained 50.1 grams of methane phosphonyl dichloride as determined by mass spectrometer analysis. V

Example 2 I When the run of Example 1 is carried out using-0.03 mole of a total catalyst mixture of about 0.005 mole of nickel iodide and about 0.05 mole. of nickel tetrakistri's chlorophosphine a better yield and selectivity ofmethane phosphonyl dichloride is observed.

Phosphine oxides and other organic phosphonyl halides which may be produced in accordance with the foregoing description and examplesare: trimethyl phosphineoxide, tripropyl phosphine oxide, dimethyl ethyl pho sphihe oxide, methyl diphenyl phosphine'oxide, methyl ethyl phenyl phosphine oxide, methyl phenyl benzyl phosphine oxide, dimethyl phosphonyl chloride, methyl ethyl phosphonyl chloride, dipropyl phosphonyl chloride, ethyl phenyl phosphonyl chloride, methyl' phenyl phosphonyl chloride, dimethyl phosphonyl bromide, methyl ethyl phosphonyl bromide, 2-chloroethane phosphonyl diehl'o ride, cyclohexane phosphonyl dichloride, tertiary butane phosphonyl dichloride and Z-chloroethane phosphonyl dl; bromide.

This invention relatesto a process of interacting an organic halide, a trivalent phosphorus halide and an' organic ether in any sequence of steps in single or multiple reaction zones and variousmodifications and alterations of procedure and operatingconditions may become ap-' parent to those skilled in the art without departing from the scope'ofthis invention. i

" Having described my' invention, I claim: 1

l. A process which comprises reacting a phosphorus trihalide, an alkyl halide having not more than 15 carbon atoms per molecule, and an alkyl ether whereinjthe ra'di cals attached to ether oxygen contain not more than 10 carbon atoms per radical and wherein ether oxyge'n is' bonded to an alkyl group and is additionally bonded'to a member of the group consisting of an unsubstituted alkyl radical and a haloalkyl radical, in the presence of a catalyst mixture comprising a metal iodide and a metal phosphorus trihalo complex having the formula M(PX3),, wherein X is halogen, M is a metal selected from the group consisting of group VI and VIII metals of the periodic table and wherein n is an integer equal to at least twice the minimum valence of M, at a temf perature between about 20 C. and about 300 C. to produce an organic phosphonyl halide.

2.The process of claim 1 in which the metal iodide of said catalyst mixture is'nickel iodide. I

A 3. The process of claim 1 in which the metal. iodide of said catalyst mixture is zinc iodide. f

4. The process of claim 1 in which the 'metal iodide of said catalyst mixture is cobalt' iodide. i

5. The process of claim 1 in which the metal phosphorustrihalo complex of the catalyst mixture is. a group VIII metal trihalo phosphinecomplex. f

6. The process of claim 1 in which the metalphos phorus trihalo complex of the catalyst .mix'tureis nickel tetrakistrichlorophosphine.

7. The process of claim 1 in which the metal phos phorus trihalo complex. of the catalyst mixture is cobalt tetrakistrichlorophosphine.

8. The process of claim 1 in which the metal 'phos phorus trihalo complex of'th'e catalyst mixture -is*nickel tetrakistribromophosphine.

9. Tl1e process of claiml in which'the metal phcs 9 phorus trihalo complex of the catalyst mixture is nickel tetrakistrifluorophosphine.

10. The process of claim 1 in which the metal phosphorus trihalocomplex of the catalyst mixture is iron pentatrichlorophosphine.

11. A process for the production of an alkane phosphonyl dichloride which comprises reacting phosphorus trichloride, an alkyl chloride having not more than fifteen carbon atoms in the alkyl group, and a saturated mono alpha-halogenated dialkyl ether having not more than ten carbon atoms in each of the alkyl groups in the presence of a catalyst mixture comprising a metal iodide and nickel tetrakistrichlorophosphine at a temperature between about 150 C. and about 275 C. for a residence time between about 1 and about 15 hours such that an alkane phosphonyl dichloride is produced, and recovering the alkanc phosphonyl dichloride as a product of the process.

12. A process for the production of methane phosphonyl dichloride which comprises reacting phosphorus trichloride, methyl chloride and alpha-chloromethyl methyl ether in the presence of a catalyst mixture comprising a metal iodide and nickel tetrakistrichlorophosphine at a temperature between about 150 C. and about 275 C. for a residence time between about 1 and about 15 hours such that methane phosphonyl dichloride is produced, and recovering the methane phosphonyl dichloride as a product of the process.

13. The process of claim 12 in which the metal iodide of said catalyst mixture is nickel iodide.

14. A process which comprises reacting a phosphorus trihalide, an alkyl halide having not more than 15 carbon atoms per molecule, and an alpha-halogenated dialkyl ether having not more than ten carbon atoms in each alkyl group bonded to ether oxygen, in the presence of a metal iodide and a metal phosphorus trihalo complex having the formula M(PX wherein X is halogen, M is a metal selected from the group consisting of group VI and group VIII metals of the periodic table, and n is an integer equal to at least twice the minimum valence of M, at a temperature between about C. and about 275 C. to produce an organic phosphonyl dihalide.

References Cited in the file of this patent UNITED STATES PATENTS 2,146,584 Lipkin Feb. 7, 1939 2,252,675 Prutton et al Aug. 12, 1941 2,276,492 Jolly et a1 Mar. 17, 1942 2,489,917 McCombie et a1 Nov. 29, 1949 2,500,022 Brown Mar. 7, 1950 2,683,168 Jensen et a1. July 6, 1954 OTHER REFERENCES Websters New International Dictionary, 2nd ed., Unabridged (1950), page 546.

Kosolapoff: Organo-phosphorus Compounds (August 1950), pages 48 and 62. 

1. A PROCESS WHICH COMPRISES REACTING A PHOSPHORUS TRIHALIDE, AN ALKYL HALIDE HAVING NOT MORE THAN 15 CARBON ATOMS PER MOLECULE, AND AN ALKYL ETHER WHEREIN THE RADICALS ATTACHED TO ETHER OXYGEN CONTAIN NOT MORE THAN 10 CARBON ATOMS PER RADICAL AND WHEREIN ETHER OXYGEN IS BONDED TO AN ALKYL GROUP AND IS ADDITIONALLY BONDED TO A MEMBER OF THE GROUP CONSISTING OF AN UNSUBSTITUTED ALKYL RADICAL AND A HALOALKYL RADICAL, IN THE PRESENCE OF A CATALYST MIXTURE COMPRISING A METAL IODINE AND A METAL PHOSPHORUS TRIHALO COMPLEX HAVING THE FORMULA M(PX3)N WHEREIN X IS A HALOGEN, M IS A METAL SELECTED FROM THE GROUP CONSISTING OF GROUP VI AND VIII METALS OF THE PERIODIC TABLE AND WHEREIN N IS AN INTEGER EQUAL TO AT LEAST TWICE THE MINIMUM VALENCE OF M, AT A TEMPERATURE BETWEEN ABOUT 20*C. AND ABOUT 300*C. TO PRODUCE AN ORGANIC PHOSPHONYL HALIDE. 